CN104979567B - A kind of preparation method of membrane electrode of fuel batter with proton exchange film - Google Patents
A kind of preparation method of membrane electrode of fuel batter with proton exchange film Download PDFInfo
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- CN104979567B CN104979567B CN201510346313.7A CN201510346313A CN104979567B CN 104979567 B CN104979567 B CN 104979567B CN 201510346313 A CN201510346313 A CN 201510346313A CN 104979567 B CN104979567 B CN 104979567B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation method of membrane electrode of fuel batter with proton exchange film, using the preparation technology of two kinds of membrane electrodes of silk-screen printing technique and ultrasonic spraying coating process, elctro-catalyst serosity I is adopted into silk-screen printing technique, elctro-catalyst serosity II is supported on PEM using ultrasonic spraying coating process is successively direct or indirect, and thus prepared membrane electrode has the catalyst layer of gradient type network structure；The present invention prepares high-performance, long-life, the multi-level, membrane electrode of gradient type network structure using the difference of binder content in different elctro-catalyst serosity；Due to the three-dimensional net structure that the fine and close structure of Catalytic Layer in thin layer electrode and ultrasound spraying are loose, the former is caused to be less than the latter by interfacial resistivity, and thin layer electrode area is quoted when Catalytic Layer effective area is guaranteed and is more than spray area, the part that thus bipolar plates are contacted with thin layer electrode during assembled battery can preferably help electronics to conduct.
Description
Technical field
The invention belongs to electrochemical field, more particularly to a kind of preparation method of membrane electrode of fuel batter with proton exchange film.
Background technology
Fuel cell (Fuel Cell) is a kind of energy conversion device, and it can be straight by the chemical energy being stored in fuel
Switch through and turn to electric energy, and do not limited by thermodynamic Carnot cycle, energy utilization rate up to more than 80%.While fuel cell is also
Have the advantages that big energy density, environmental friendliness, low noise, high safety, cruising time length, scope on probation are wide, extensively used
In middle-size and small-size electric station, portable communications power supply, family cogenerator, field depopulated zone detection power supply, civil car,
The aspects such as Aero-Space, the electrical source of power of submarine.
MEA (Membrane Electrode Assembly) is also called membrane electrode, is the heart of fuel cell, by CCM
(catalyst coat film) is constituted with three part of Yin/Yang pole diffusion layer, and diffusion layer plays water management, the distribution of material, transmission electronics
Deng effect, CCM is the main place of electrochemical reaction, is related to the problems such as transmission and discharge of the generation and product for reacting, MEA
Used as the elementary cell of electrochemical reaction of fuel battery, its design and preparation first has to follow electrochemical reaction of fuel battery
Ultimate principle and characteristic, and the use condition final with fuel cell, economic benefit and preparation technology etc. combine to carry out
Consider.Different process will also determine that the service behaviour of fuel cell, service life, auxiliary facility etc. are a series of to closing
Important problem.The membrane electrode that at present prepared by spraying process is widely used, Wang Xindong, Liu Guicheng et al. due to its superior performance
A kind of temperature field is adopted in patent CN103000912A to control the volatilization of solvent in ultrasonic spraying process serosity, preparation
MEA is used for DMFC；Jay S.Hulett et al. are also adopted by spraying process in US6074692A by the serosity
Spray on the film drawn by clamping plate.But the shortcoming of spraying process is that performance degradation is fast, catalyst utilization is low, preparation technology energy
Consume big etc., cause this kind of technique to be adapted to small lot batch manufacture；The WG O'Brien of du pont company are in patent WO0243171A2
The aniline raised relief of middle employing is printed for preparing fuel cell membrane electrode on a large scale, and the serosity is driven with anilox roll
To in letterpress, letterpress platform then being adjusted to the distance of film, Catalytic Layer being printed onto on film, film is then by traction machine
Traction, realizes large-scale production, has the disadvantage complex process, poor controllability, affected by environment big, poor repeatability；U.S. Loews Ah
The thin layer electrode method that wilson of this National Key Laboratory of Rameau et al. is proposed in patent US5234777A prepares fuel electricity
Pond membrane electrode, using vacuum sputtering it is direct or indirect prepare membrane electrode, so-called direct thin layer electrode method refers to serosity is straight
Connect and be splashed on ion exchange membrane, and thin layer electrode method is exactly so-called decalcomania (Decal) indirectly, and serosity is splashed to transfer
On medium and then the catalyst on medium is transferred on ion exchange membrane, as the shortcoming of sputtering method is projected, in recent years
Progressively substituted, but the preparation thinking of thin layer electrode is but widely studied always；Ion Power companies of the U.S.
Stephen Andreas Grot et al. are exactly to employ the decalcomania in thin layer electrode in its patent US6641862B1, together
When they scribble a leafing sub-exchange resin (Nafion) on the applique surface for being loaded with catalyst, formed together with film hot pressing
CCM does not use film directly to form CCM by the transfer applique hot pressing for being loaded with catalyst and ion exchange resin；This patent is sent out
A person of good sense uses for reference the indirect thin layer electrode method in the thin layer electrode method of wilson et al., prepares the applique using silk-screen printing technique
(Decal), then together with film hot pressing, thin layer electrode after tearing offset medium, is formed, the advantage of this kind of method is exist
Hot pressing, the advantage of hot pressing are to cause Catalytic Layer and the combination of film more firmly to reduce the leafing phenomenon raising life-span, when
Nafion ion exchange resin when temperature reaches the glass transition temperature of Nafion ion exchange resin in molten condition
The central increase mass transfer of hole of catalyst, and the meeting of Nafion ion exchange resin and the Nafion membrane bonding shape of melting can be entered
Into covalent bond, compare the Van der Waals force adhesion formed under the simple accumulation mode of catalyst in conventional spray paint technique and be eager to excel, heat
Membrane electrode after pressure is essentially without there is leafing phenomenon, while the high Nafion ion exchange resin that inventor herein adopts
The serosity of content (35%～50%) is used in thin layer electrode, according to similar compatibility principle, it will further increase transfer legal system
The adhesion of standby Catalytic Layer and film, under same catalyst carrying capacity, the thickness of thin layer electrode reduction Catalytic Layer can be reduced in addition
The distance of proton transport, improves membrane electrode performance, while thin layer electrode prepared by this patent is also the serosity of follow-up spraying coating process
Support and play a part of a transition.
Additionally, the research of multi-layered electrode is also by extensive concern, S.Y.Cha and W.M.Lee et al. are in article
“Performance of proton exchange membrane fuel cell electrodes prepared by
Phase is elaborated in dorect decomposition of ultrathin platinum on the membrane surface "
Under with catalyst loading, it is better than the performance of the electrode layer of single thickness using the performance of multiple thin layer electrodes；Korea Yung-Eun
Sung seminars delivered the several methods with regard to preparing fuel cell membrane electrode using multi-layered electrode, wherein in turning to overlay and spend
Add carbon-coating to increase the rate of transform of catalyst and add carbon-coating to reduce the first in methanol fuel cell in the middle of the Catalytic Layer
The methods such as alcohol infiltration are suggested；Additionally, also research worker prepares two-layer electrode using one layer of platinum black, one layer of pallium-on-carbon
Method, in the Catalytic Layer for obtaining, the content of noble metal is presented gradient type distribution, and conclusion is that the performance of this electrode is better than and wherein appoints
The performance of meaning component single-layer electrodes, i.e. gradient type catalyst deposit (Graded catalyst deposition) are studied,
C.A.Cavalca et al. combines thin layer electrode method in patent US6300000B1 and vacuum sputtering prepares gradient Catalytic Layer, adopts
With electro beam physics vapour deposition by unitary or binary metal catalyst deposit on thin layer electrode, hydrogen reduction can be reduced anti-
The overpotential answered, under high electric density, performance is superior；E.A.Ticianelli et al. is in article " Localization of
platinum in low catalyst loading electrodes to attain high power densities in
Vacuum sputtering is also adopted by SPE fuel cells " catalyst is splashed on the electrode of politef-bound, is drawn
The high performance membrane electrode of low carrying capacity.The gradient that both the above method is related to refers to that noble metal catalyst is presented ladder inside Catalytic Layer
Degree formula is distributed, and this patent uses for reference multi-level, the preparation thought of gradient type electrode, with reference to existing spraying coating process and screen printing dataller
Gradient type network distribution structure is introduced into increase Catalytic Layer active area in Catalytic Layer, reduces the overpotential of oxygen reduction reaction by skill,
Hole between the multilamellar that described gradient type network distribution structure is related in referring to Catalytic Layer is different and cause the pore structure to be in
Existing gradient type is distributed (see Fig. 3).
Further, since the loose three-dimensional net structure of the fine and close structure of Catalytic Layer and spraying process in thin layer electrode, before causing
Person's interfacial resistivity is less than the latter, and thin layer electrode area is quoted when Catalytic Layer effective area is guaranteed and is more than spray area, by
The part that bipolar plates are contacted with thin layer electrode during this assembled battery can preferably help electronics to conduct.
Membrane electrode life problems are also widely studied, and Th.Frey and M.Linardi is in its entitled " Effects of
membrane electrode assembly preparation on the polymer electrolyte membrane
Elaborate that the influence factor of membrane electrode performance depends primarily on the selection of material in fuel cell performance " articles
And application, next to that the optimization of technique, while it is that membrane electrode is transported through prolonged that they also refer to the influence factor in life-span
Row (more than 500 hours) occurs leafing phenomenon, causes performance drastically to decline, and the membrane electrode operation 500 after hot pressing is little
When do not observe leafing phenomenon, illustrate that hot pressing improves well the life-span of membrane electrode；Entitled " the Microscopic of Z.X.Liang et al.
characterizations of membrane electrode assemblies prepared under different
The article of hot-pressing conditions " is using means such as XPS, XRD, FT-IR, ECSA, acceleration leafing to membrane electrode heat
The research changed before and after pressure, including anode and cathode Catalytic Layer, Nafion membrane etc. carry out comparative illustration, have drawn hot pressing to membrane electrode
The impact of energy less, but can be to improve its life-span, and leafing phenomenon is not observed after membrane electrode runs 1000 hours.This patent
Using thin layer electrode preparation process in employ hot pressing process, exactly in order to improve the membrane electrode life-span, reduce membrane electrode and exist
Generation of the catalyst layer after long-play from phenomenon.
In sum, inventor herein thinks that membrane electrode of fuel batter with proton exchange film excessively depends on material itself,
Next to that the optimization of preparation technology, on the basis of material is similar, is difficult to meet film electricity in fuel cell by single technique
Extremely harsh task (entrance of reactant, the exclusion of product etc.), the combination of kinds of processes and Catalytic Layer it is interior
The optimization of portion's structure and noble metal catalyst distribution will be requisite, in economical efficiency of the preparation technology with reality
A balance can be reached eventually.
The content of the invention
Goal of the invention：The invention provides a kind of preparation method of membrane electrode of fuel batter with proton exchange film, existing to solve
The membrane electrode preparation technology for having the employing in technology single is difficult to meet the entrance of reactant in fuel cell membrane electrode and generation
The problem that thing is excluded；As the membrane electrode performance prepared using silk-screen printing technique is not high, prepared using ultrasonic spraying coating process
Membrane electrode performance degradation is fast, catalyst utilization is low, preparation technology energy consumption big, so two kinds of techniques are combined next gram by the present invention
Take every kind of technique and the problem produced by membrane electrode is manufactured separately.
Technical scheme：To achieve these goals, the present invention is employed the following technical solutions：
A kind of preparation method of membrane electrode of fuel batter with proton exchange film, by silk-screen printing technique and ultrasonic spraying coating process two
The preparation technology for planting membrane electrode combines, and elctro-catalyst serosity I is transferred to PEM initially with silk-screen printing technique
On, form thin layer electrode；Elctro-catalyst serosity II is sprayed directly on thin layer electrode using ultrasonic spraying coating process again, formation is urged
Agent coated film, then catalyst coat film is carried out into edge sealing, then will be placed on the diffusion layer of the commercialization of Catalytic Layer homalographic and urge
Change layer both sides, make the membrane electrode with gradient type network structure Catalytic Layer；
The silk-screen printing technique is the elctro-catalyst serosity I containing catalyst that will be prepared in advance using screen process press
It is screen-printed on offset medium, is prepared into transfer applique, then the catalyst that will be formed by elctro-catalyst serosity I on transfer applique
Layer I is transferred on PEM by hot press hot pressing mode, tears offset medium, forms thin layer electrode, thin layer electrode
Thickness is 3～10 μm；
The ultrasonic spraying coating process is, using ultrasound spraying instrument direct spraying, thin layer electrode to be layered on vacuum cup, then
The advance elctro-catalyst serosity II prepared is sprayed directly on thin layer electrode, catalyst layer II, shape are formed on thin layer electrode
Into catalyst coat film CCM.
Further, the compound method of the elctro-catalyst serosity I is：By catalyst, stabilizer, diluent, thickening agent,
Binding agent, cosolvent are 1 according to mass ratio：2～5：4～15：0.5～2：10～30：0.5～2 mixing, control solid content exist
Between 6.5～7.5%, dynamic viscosity value is 30mPas～55mPas, and the wherein ion exchange resin in binding agent accounts for electricity
The 35～60% of I dry weight of catalyst slurry, then make serosity mix homogeneously using sonic oscillation and emulsification pretreatment.
Preferably, the parameter of the hot press hot pressing is 115 DEG C～140 DEG C of temperature, pressure 130kg/cm2～200kg/
cm2, hot pressing time be 30s～5min.
Preferably, the offset medium be polytetrafluoroethylene film, aluminium foil, any one in Kapton.
Further, the compound method of the elctro-catalyst serosity II is：By catalyst, stabilizer, diluent, bonding
Agent, cosolvent are 1 according to mass ratio：2～5：20～40：2.2～6.6：0.5～2 mixing；Control solid content 2～3.5% it
Between, dynamic viscosity value is 5mPas～15mPas, and wherein binding agent ion exchange resin accounts for II dry weight of elctro-catalyst serosity
10～25% between, then mix serosity using sonic oscillation and emulsification pretreatment equal.
Binder content in the preferred elctro-catalyst serosity I is higher than elctro-catalyst serosity II.
Preferably, in direct spraying, temperature remains 60 DEG C～95 DEG C, and vacuum is 0.1atm～0.5atm.
Further, the gradient type network structure is by ion exchange resin and II institute of catalyst layer I and catalyst layer
The three-dimensional net structure of composition, the catalyst layer I for being arranged from PEM from inside to outside and catalyst layer II formula net in gradient
Network structure.
Further, the gradient type network be catalyst layer I to catalyst layer II electrochemistry specific surface area according to
Secondary increase, appearance features are that porosity is increased to catalyst layer II successively by catalyst layer I；The catalyst of catalyst layer I and viscous
Knot dosage form into granule it is higher than the granule closeness that catalyst layer II is formed.
A kind of membrane electrode of fuel batter with proton exchange film, including PEM, the both sides of the PEM are all provided with
Catalyst layer I is equipped with, catalyst layer II on the outside of the catalyst layer I, is provided with.
Beneficial effect：A kind of preparation method of membrane electrode of fuel batter with proton exchange film proposed by the present invention, solves silk
Not enough problem when net typography and ultrasonic two kinds of techniques of spraying coating process are manufactured separately；Glue using in different elctro-catalyst serosity
The difference of knot agent content prepares high-performance, long-life, the multi-level, membrane electrode of gradient type network structure；
Hot pressing is effectively increased the adhesion between Catalytic Layer and PEM, and hot pressing can be offset after carrying out hot pressing
When PEM thickness loss, reduce the byproduct of reaction hydrogen peroxide that the interface of Catalytic Layer and PEM produces
Attack of the group to film, and then delay the degradation rate of film, improve the membrane electrode life-span, it is to avoid membrane electrode is through long-play
Catalyst layer afterwards is from phenomenon；
The advantage of hot pressing is to cause Catalytic Layer and the combination of PEM more firmly to reduce the raising of leafing phenomenon
Life-span, the ion exchange resin when temperature reaches the glass transition temperature of ion exchange resin in molten condition can enter
Increase mass transfer in the middle of the hole of catalyst, and the ion exchange resin for melting can bond together to form covalent bond with PEM,
Compare the Van der Waals force adhesion formed under the simple accumulation mode of catalyst in conventional spray paint technique to be eager to excel, the film electricity after hot pressing
Pole is not in leafing phenomenon；
The elctro-catalyst serosity I of the higher ion exchange resin content that this patent is adopted is used in thin layer electrode, according to
Similar compatibility principle, it will further increase the Catalytic Layer of silk-screen printing technique preparation and the adhesion of ion exchange membrane, in addition
Under same catalyst carrying capacity, the thickness of thin layer electrode reduction Catalytic Layer can reduce the distance of proton transport, improve membrane electrode
Energy；Thin layer electrode prepared by this patent is also supported and plays a transition for the elctro-catalyst serosity II of subsequent ultrasonic spraying coating process
Effect；
With reference to silk-screen printing technique and ultrasonic spraying coating process, the hole between the multilamellar being related in Catalytic Layer is different and cause
Pore structure is presented gradient type distribution, and gradient type network distribution structure is introduced into increase Catalytic Layer active area in Catalytic Layer, drop
The overpotential of hypoxia reduction reaction.
Further, since the loose three-dimensional net structure of the fine and close structure of Catalytic Layer and ultrasound spraying in thin layer electrode, causes
The former interfacial resistivity is less than the latter, and thin layer electrode area is quoted when Catalytic Layer effective area is guaranteed and is more than spray area,
Thus the part that bipolar plates are contacted with thin layer electrode during assembled battery can preferably help electronics to conduct；From in terms of microcosmic angle,
The network structure of this progressive formula preferably can solve the generation of reactant, the discharge of product, the transfer of electronics with
And the transmission of proton etc. affects the subject matter of membrane electrode performance.
Description of the drawings
Fig. 1 is the process chart of the present invention；
Fig. 2 is the internal structure schematic diagram of inventive film electrode；
Fig. 3 is the surface topography of Catalytic Layer of the present invention I；
Fig. 4 is the surface topography of Catalytic Layer of the present invention II；
Fig. 5 is the IV performance charts of the embodiment of the present invention 1, comparative example 1 and comparative example 2；
Wherein：1- PEMs, 2- Catalytic Layers I, 3- Catalytic Layers II, 4- thin layer electrodes, 5- catalyst coat film CCM.
Specific embodiment
The present invention is further described with reference to embodiment.
A kind of membrane electrode of fuel batter with proton exchange film, including PEM 1, the both sides of the PEM 1 are equal
Catalyst layer I 2 is provided with, catalyst layer II 3 on the outside of the catalyst layer I 2, is provided with.
Elctro-catalyst serosity I is adopted screen printing dataller by a kind of preparation method of membrane electrode of fuel batter with proton exchange film
Skill is indirectly supported on the both sides of PEM 1, is prepared into thin layer electrode 4；Then by elctro-catalyst serosity II using ultrasound
Spraying coating process is sprayed on the outside of thin layer electrode 4, elctro-catalyst serosity II is directly supported on the outside of thin layer electrode 4, system
Into catalyst coat film CCM5.
Embodiment 1
A kind of preparation method of membrane electrode of fuel batter with proton exchange film, comprises the following steps,
Step one, prepare elctro-catalyst serosity I
60%Pt/C catalyst is weighed, the mixed of catalyst, stabilizer water, slurry dilution agent ethanol and isopropanol is sequentially added
Bonding solvent (1:1), thickening agent ethylene glycol, 5% amberlite lipoprotein solution of binding agent, cosolvent dimethyl sulfoxide, six kinds of the above
The mass ratio of composition is to be fixed on 1：2：6.8：0.5：20：0.5, its ion exchange resin accounts for I dry weight of elctro-catalyst serosity
50%, adjustment other components metering ratio, solid content are maintained at 6.5%, and ultrasonic agitation 60 minutes after mixing is then placed in emulsifying
Machine, emulsified 30 minutes in 13000r/min, dynamic viscosity value is 55mPas, sealing, is preserved at 10 DEG C；
Step 2, prepare silk-screen printing technique and prepare thin layer electrode
A. screen printing apparatus are adjusted, will be with 6*6cm2The screen frame of effectively silk screen size is fixed, and mixes up screen frame table
The levelness in face, silk screen adopt stainless (steel) wire, and mesh is 200 mesh.
B. by 6*6cm2Offset medium Kapton be positioned on the vacuum suction table of printing platform, adjustment transfer be situated between
Matter is consistent with the effective area of silk screen, i.e. the effective area and offset medium of silk screen overlap.
C. screen frame is transferred on printing platform, then by appropriate slurry drops before the scraper of effective silk screen area
Scraper is transferred to screen frame surface by end, by elctro-catalyst serosity I on silk screen surface brush 4 times.
D. after having brushed 4 times, weigh, be dried.Repeat step C, you can the catalyst layer of loading, the expensive gold of anode needed for obtaining
Category 0.1 ± 0.01mg/cm of carrying capacity2, negative electrode 0.2 ± 0.01mg/cm of noble metal carrying capacity2。
E. the transfer applique that finishes will be brushed and is put in baking oven 60 DEG C of dryings 12 hours；
F. the above-mentioned transfer applique for preparing is taken out into (anode 0.1 ± 0.01mg/cm of noble metal carrying capacity2, negative electrode noble metal
0.2 ± 0.01mg/cm of carrying capacity2), then transfer applique is alignd with the center of PEM, is clamped with mirror board, is sent
Entering hot press carries out hot pressing, hot pressing condition：Pressure 200kg/cm2, 140 DEG C of temperature, hot pressing time 30s, transfer hot pressing form thin
Layer electrode, Catalytic Layer thickness tear offset medium between 3～10 μm.
Step 3, prepare elctro-catalyst serosity II
60%Pt/C catalyst is weighed, catalyst stabilizer water, slurry dilution agent ethanol and isopropanol (1 is sequentially added:1)
Mixed solvent, binding agent amberlite lipoprotein solution, cosolvent dimethyl sulfoxide, the mass ratio of five kinds of compositions of the above are 1：2：
34：6.6：0.5, solid content is maintained between 3%, and its ion exchange resin accounts for the 25% of II dry weight of elctro-catalyst serosity, is mixed
Ultrasonic agitation 60 minutes after conjunction, then mulser 13000r/min emulsified 30-60 minutes, dynamic viscosity value is 10mPas,
Sealing, preserves at 10 DEG C；
Step 4, spraying form catalyst coat film
The elctro-catalyst serosity combination II for preparing is loaded in the injector of spraying instrument, opening operation program, will step
The thin layer electrode prepared in rapid two is layered on spraying area, and fixture is fixed, and is kept for 95 DEG C (less than the glass transition temperature of film
97 DEG C), vacuum pump is opened, vacuum is sprayed in 0.1atm, every time the carrying capacity substantially 0.1mg/cm of spraying2, so
Thin layer electrode anode is sprayed 1 time, and thin layer electrode negative electrode is sprayed 2 times and be can reach and 2 identical catalyst of comparative example 1 and comparative example
Carrying capacity, i.e. 0.2 ± 0.01mg/cm of anode noble metal carrying capacity2, negative electrode 0.4 ± 0.01mg/cm of noble metal carrying capacity2。
Embodiment 2
A kind of preparation method of membrane electrode of fuel batter with proton exchange film, comprises the following steps,
Step one, prepare elctro-catalyst serosity I
60%Pt/C catalyst is weighed, catalyst, stabilizer water, diluent ethanol and isopropanol (1 is sequentially added:1)
Mixed solvent, thickening agent ethylene glycol, 5% amberlite lipoprotein solution of binding agent, cosolvent dimethyl sulfoxide, six kinds of compositions of the above
Mass ratio be 1：2：5：0.5：30：0.5, its ion exchange resin accounts for the 60% of I dry weight of elctro-catalyst serosity, adjusts other
Component metering ratio, solid content are maintained at 6.5%, and ultrasonic agitation 30 minutes after mixing is then placed in mulser, in 13000r/min
Emulsified 30 minutes, dynamic viscosity value was 30mPas, sealing, was preserved at 10 DEG C；
Step 2, prepare thin layer electrode (thin-film electrode)
A. screen printing apparatus are adjusted, will be with 6*6cm2The screen frame of effectively silk screen size is fixed, and mixes up screen frame table
The levelness in face, silk screen adopt stainless (steel) wire, and mesh is 200 mesh.
B. by 6*6cm2Offset medium aluminium foil be positioned on the vacuum suction table of printing platform, adjustment offset medium with silk screen
Effective area it is consistent, i.e. the effective area and offset medium of silk screen overlap.
C. screen frame is transferred on printing platform, elctro-catalyst serosity I is dripped into scraping in effective silk screen area then
Scraper is transferred to screen frame surface by knife front end, by elctro-catalyst serosity I on silk screen surface brush 4 times.
D. repeat step C, you can the catalyst layer of loading needed for obtaining, transfer applique anode noble metal carrying capacity are 0.1
±0.01mg/cm2, negative electrode noble metal carrying capacity is 0.2 ± 0.01mg/cm2。
E. the transfer applique that finishes will be brushed and be put in baking oven 60 DEG C of dryings 12 hours, you can thin layer is prepared for turning platen press
Electrode.
F. the above-mentioned transfer applique for preparing is taken out into (anode 0.1 ± 0.01mg/cm of noble metal carrying capacity2, negative electrode noble metal
0.2 ± 0.01mg/cm of carrying capacity2), then transfer applique is alignd with the center of PEM, is clamped with mirror board, is sent
Entering hot press carries out hot pressing, hot pressing condition：Pressure 130kg/cm2, 115 DEG C of temperature, hot pressing time 5min, transfer hot pressing form thin
Layer electrode, Catalytic Layer thickness tear offset medium between 3～10 μm.
Step 3, prepare elctro-catalyst serosity II
60%Pt/C catalyst is weighed, the mixing for sequentially adding catalyst, stabilizer water, diluent ethanol and isopropanol is molten
Agent (1:1), binding agent amberlite lipoprotein solution, cosolvent dimethyl sulfoxide, the mass ratio of five kinds of compositions of the above is 1：2：34：
6.6：0.5, solid content is maintained between 3%, and its ion exchange resin accounts for the 25% of II dry weight of elctro-catalyst serosity, after mixing
Ultrasonic agitation 30 minutes, then mulser 13000r/min is emulsified 30 minutes, and dynamic viscosity value is 10mPas, sealing, and 10
Preserve at DEG C；
Step 4, spraying form catalyst coat film
The elctro-catalyst serosity combination II for preparing is loaded in the injector of spraying instrument, opening operation program, will step
The thin layer electrode prepared in rapid two is layered on spraying area, and fixture is fixed, and is kept for 60 DEG C (less than the glass transition temperature of film
97 DEG C), vacuum pump is opened, vacuum is sprayed in 0.5atm, and the carrying capacity of spraying is 0.1mg/cm every time2, so in thin layer
Electrode anode is sprayed 1 time, and thin layer electrode negative electrode sprays 2 times and can reach and comparative example 1 and 2 identical catalyst of comparative example load
Amount, i.e. 0.2 ± 0.01mg/cm of anode noble metal carrying capacity2, negative electrode 0.4 ± 0.01mg/cm of noble metal carrying capacity2。
Embodiment 3
A kind of preparation method of membrane electrode of fuel batter with proton exchange film, comprises the following steps,
Step one, prepare elctro-catalyst serosity I
60%Pt/C catalyst is weighed, catalyst, stabilizer water, diluent ethanol and isopropanol (1 is sequentially added:1)
Mixed solvent, thickening agent ethylene glycol, 5% amberlite lipoprotein solution of binding agent, cosolvent dimethyl sulfoxide, six kinds of compositions of the above
Mass ratio be 1：2：4：2：10.8：0.5, its ion exchange resin accounts for the 35% of I dry weight of elctro-catalyst serosity, adjusts other
Component metering ratio, solid content are maintained at 7.5%, and ultrasonic agitation 30 minutes after mixing is then placed in mulser, in 13000r/min
Emulsified 30 minutes, dynamic viscosity value was 55mPas, sealing, was preserved at 10 DEG C；
Step 2, prepare thin layer electrode (thin-film electrode)
A. screen printing apparatus are adjusted, will be with 6*6cm2The screen frame of effectively silk screen size is fixed, and mixes up screen frame table
The levelness in face, silk screen adopt stainless (steel) wire, and mesh is 200 mesh.
B. by 6*6cm2Offset medium polytetrafluoroethylene film be positioned on the vacuum suction table of printing platform, adjustment transfer
Medium is consistent with the effective area of silk screen, i.e. the effective area and offset medium of silk screen overlap.
C. screen frame is transferred on printing platform, elctro-catalyst serosity I is dripped into scraping in effective silk screen area then
Scraper is transferred to screen frame surface by knife front end, by elctro-catalyst serosity I on silk screen surface brush 4 times.
D. repeat step C, you can the catalyst layer of loading needed for obtaining, transfer applique anode noble metal carrying capacity are 0.1
±0.01mg/cm2, negative electrode noble metal carrying capacity is 0.2 ± 0.01mg/cm2。
E. the transfer applique that brushing is finished is put in into the drying 12 hours of 80 DEG C of baking oven, you can thin-layer electric is prepared for turning platen press
Pole.
F. the above-mentioned transfer applique for preparing is taken out into (anode 0.1 ± 0.01mg/cm of noble metal carrying capacity2, negative electrode noble metal
0.2 ± 0.01mg/cm of carrying capacity2), then transfer applique is alignd with the center of PEM, is clamped with mirror board, is sent
Entering hot press carries out hot pressing, hot pressing condition：Pressure 200kg/cm2, 140 DEG C of temperature, hot pressing time 30s, transfer hot pressing form thin
Layer electrode, I thickness of catalyst layer tear offset medium between 3～10 μm.
Step 3, prepare elctro-catalyst serosity II
60%Pt/C catalyst is weighed, catalyst, stabilizer water, diluent ethanol and isopropanol (1 is sequentially added:1)
Mixed solvent, binding agent amberlite lipoprotein solution, cosolvent dimethyl sulfoxide, the mass ratio of five kinds of compositions of the above is 1：2：
34：6.6：0.5, solid content is maintained at 3%, and its ion exchange resin accounts for the 25% of II dry weight of elctro-catalyst serosity, after mixing
Ultrasonic agitation 30 minutes, then mulser 13000r/min is emulsified 30 minutes, and dynamic viscosity value is 10mPas, sealing, and 10
Preserve at DEG C；
Step 4, spraying form catalyst coat film
The elctro-catalyst serosity combination II for preparing is loaded in the injector of spraying instrument, opening operation program, will step
The thin layer electrode prepared in rapid two is layered on spraying area, and fixture is fixed, and is kept for 95 DEG C (less than the glass transition temperature of film
Degree), vacuum pump is opened, vacuum is sprayed in 0.1atm, and the carrying capacity of spraying is 0.1mg/cm every time2, so in thin-layer electric
Pole anode is sprayed 1 time, and thin layer electrode negative electrode is sprayed 2 times and be can reach and 2 identical catalyst loading of comparative example 1 and comparative example,
That is 0.2 ± 0.01mg/cm of anode noble metal carrying capacity2, negative electrode 0.4 ± 0.01mg/cm of noble metal carrying capacity2。
Comparative example 1：Serigraphy process prepares thin layer electrode (thin-film electrode)
The step of serigraphy process prepares thin layer electrode be：
First, elctro-catalyst serosity is prepared, 60%Pt/C catalyst is weighed, catalyst stabilizer water, diluent is sequentially added
Ethanol and isopropanol (1:1) mixed solvent, thickening agent ethylene glycol, binding agent amberlite lipoprotein solution, cosolvent dimethyl
Sulfoxide, the mass ratio of six kinds of compositions is 1：2：10：0.5：6.6：0.5, solid content is maintained at 6.5%, its ion exchange resin
The 25% of elctro-catalyst serosity dry weight is accounted for, ultrasonic agitation 30 minutes after mixing, then mulser 13000r/min is emulsified 30 points
Clock, viscosity number are maintained at 30-55mPas, sealing, preserve at 10 DEG C；
2nd, silk-screen printing technique prepares transfer applique, 1. adjusts screen printing apparatus, will be with 6*6cm2Effective silk screen
The screen frame of size is fixed, and mixes up the levelness on screen frame surface, and silk screen adopts the stainless (steel) wire, mesh to be：200 mesh；2. by 6*
6cm2Offset medium polytetrafluoroethylene film is positioned on the vacuum suction table of printing platform, and adjustment offset medium is with the effective of silk screen
Area is consistent, i.e. the effective area and offset medium of silk screen overlap；3. screen frame is transferred on printing platform, then by electricity
Catalyst slurry I is dripped in the scraper front end on effective silk screen area one side, and scraper is transferred to screen frame surface, by elctro-catalyst serosity
I on silk screen surface brush 4 times；4. after having brushed 4 times, weigh, be dried；5. repeat step 3 and 4, you can loading urges needed for obtaining
Agent layer I, anode noble metal carrying capacity are 0.2 ± 0.01mg/cm2, negative electrode noble metal carrying capacity is 0.4 ± 0.01mg/cm2；6. will brush
The transfer applique that finishes of painting is put in baking oven 80 DEG C of dryings 12 hours, you can for preparing catalyst coat film.
3rd, the above-mentioned transfer applique for preparing is taken out into (anode 0.2 ± 0.01mg/cm of noble metal carrying capacity2, the expensive gold of negative electrode
Category 0.4 ± 0.01mg/cm of carrying capacity2), then transfer applique is alignd with the center of PEM, is clamped with mirror board,
Sending into hot press carries out hot pressing, and hot pressing condition is pressure 190kg/cm2, 135 DEG C of temperature, hot pressing time 5min are saved backup.
Comparative example 2：Ultrasonic spraying coating process prepares catalyst coat film
Ultrasonic spraying coating process prepares catalyst coat film and comprises the following steps：
First, elctro-catalyst serosity is prepared, 60%Pt/C catalyst is weighed, catalyst stabilizer water, diluent is sequentially added
Ethanol and isopropanol (1:1) mixed solvent, 5% amberlite lipoprotein solution of binding agent, cosolvent dimethyl sulfoxide, the above five
The mass ratio for planting composition is 1：2：34：6.6：0.5, solid content is maintained at 3%, and its ion exchange resin accounts for elctro-catalyst serosity
The 25% of dry weight, ultrasonic agitation 30 minutes after mixing, then mulser 13000r/min is emulsified 30 minutes, and viscosity number is maintained at
5-10mPas, sealing are preserved at 10 DEG C；
2nd, spraying forms catalyst coat film, and above-mentioned configuration good elctro-catalyst serosity is loaded the injector of spraying instrument
In, film is layered on spraying area by opening operation program, and fixture is fixed, and is kept for 80 DEG C (less than the glass transition temperature 97 of film
DEG C), vacuum pump is opened, vacuum is sprayed between 0.35atm, and the carrying capacity of spraying is 0.1mg/cm every time2, so positive
Pole sprays twice, and negative electrode is sprayed four times, is saved backup.
The catalyst coat film prepared in embodiment 1, comparative example 1 and comparative example 2 is assembled into battery carries out test comparison：
The catalyst coat film that embodiment 1, comparative example 1 and comparative example 2 are prepared is carried out into edge sealing, then together with diffusion layer
Assembled battery together, takes effective area for 5*5cm2, test condition：Hydrogen is 0.04Mpa, and oxygen stoichiometric proportion is 7.2, electricity
Pond temperature 50 C, 25 DEG C of cathode humidification temperature.
As shown in figure 4, the membrane electrode prepared using three kinds of different membrane electrode preparation technologies is contrast experiment, wherein：It is right
Membrane electrode in ratio 1 and comparative example 2 prepares scheme and all has been directed in previous literature, brings herein and present invention proposition
Method for preparing membrane electrode prepare membrane electrode embodiment do with contrast.
Analytic explanation：Dependence Results from Fig. 4 can be seen that comparative example 1 adopts membrane electrode prepared by serigraphy process
Can be relatively poor, because PEM is relatively dry, mass transfer serious polarization, but open-circuit voltage is super than adopting in comparative example 2
Membrane electrode prepared by sound spraying coating process is high, the performance of the membrane electrode prepared using the method that the present invention is provided in embodiment 1 and right
The membrane electrode prepared using ultrasonic spraying coating process in ratio 2, in 800mA/cm2Under it is essentially identical, but in embodiment 1 using this
The membrane electrode that the open-circuit voltage of membrane electrode prepared by the method that invention is provided is prepared higher than other two methods, this is for membrane electrode
The raising in life-span is very helpful, and from terms of existing result, effectively increases the service life of membrane electrode.
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of membrane electrode of fuel batter with proton exchange film, it is characterised in that by silk-screen printing technique and ultrasound
The preparation technology of two kinds of membrane electrodes of spraying coating process combines, and is transferred to elctro-catalyst serosity I initially with silk-screen printing technique
On PEM, thin layer electrode is formed；Elctro-catalyst serosity II is sprayed directly into by thin-layer electric using ultrasonic spraying coating process again
Extremely go up, form catalyst coat film, then catalyst coat film is carried out into edge sealing, then by the expansion with the commercialization of Catalytic Layer homalographic
Scattered layer is placed on Catalytic Layer both sides, makes the membrane electrode with gradient type network structure Catalytic Layer；
The silk-screen printing technique is I silk screen of elctro-catalyst serosity containing catalyst that will be prepared in advance using screen process press
It is printed onto on offset medium, is prepared into transfer applique, then the catalyst layer I that will be formed by elctro-catalyst serosity I on transfer applique
It is transferred on PEM by hot press hot pressing mode, tears offset medium, forms thin layer electrode, the thickness of thin layer electrode
For 3 ~ 10 μm；
The ultrasonic spraying coating process is, using ultrasound spraying instrument direct spraying, thin layer electrode to be layered on vacuum cup, then will be pre-
The elctro-catalyst serosity II first prepared is sprayed directly on thin layer electrode, and catalyst layer II is formed on thin layer electrode, and formation is urged
Agent coated film CCM.
2. the preparation method of membrane electrode of fuel batter with proton exchange film according to claim 1, it is characterised in that the electricity
The compound method of catalyst slurry I is：By catalyst, stabilizer, diluent, thickening agent, binding agent, cosolvent according to mass ratio
For 1：2~5：4~15：0.5~2：10~30：0.5 ~ 2 mixing, between 6.5 ~ 7.5%, dynamic viscosity value is control solid content
Ion exchange resin in 30mPas ~ 55mPas, wherein binding agent accounts for the 35 ~ 60% of I dry weight of elctro-catalyst serosity, then
Serosity mix homogeneously is made using sonic oscillation and emulsification pretreatment.
3. the preparation method of membrane electrode of fuel batter with proton exchange film according to claim 1, it is characterised in that the heat
The parameter of press hot pressing is 115 DEG C ~ 140 DEG C of temperature, pressure 130kg/cm2~200kg/cm2, hot pressing time be 30s ~ 5min.
4. the preparation method of membrane electrode of fuel batter with proton exchange film according to claim 1, it is characterised in that described turn
Print medium is polytetrafluoroethylene film, aluminium foil, any one in Kapton.
5. the preparation method of membrane electrode of fuel batter with proton exchange film according to claim 1, it is characterised in that the electricity
The compound method of catalyst slurry II is：It is 1 according to mass ratio by catalyst, stabilizer, diluent, binding agent, cosolvent：2~
5：20~40：2.2~6.6：0.5 ~ 2 mixing；Between 2 ~ 3.5%, dynamic viscosity value is 5mPas ~ 15mPa to control solid content
S, wherein binding agent ion exchange resin are accounted between the 10 ~ 25% of II dry weight of elctro-catalyst serosity, then using sonic oscillation and
It is equal that emulsification pretreatment mixes serosity.
6. the preparation method of the membrane electrode of fuel batter with proton exchange film according to claim 2 or 5, it is characterised in that institute
It is higher than elctro-catalyst serosity II to state the binder content in elctro-catalyst serosity I.
7. the preparation method of membrane electrode of fuel batter with proton exchange film according to claim 1, it is characterised in that direct
During spraying, temperature remains 60 DEG C ~ 95 DEG C, and vacuum is 0.1atm ~ 0.5atm.
8. the preparation method of membrane electrode of fuel batter with proton exchange film according to claim 1, it is characterised in that the ladder
Degree formula network structure is the three-dimensional net structure being made up of ion exchange resin and catalyst layer I and catalyst layer II, from matter
Catalyst layer I that proton exchange is arranged from inside to outside and catalyst layer II formula network structure in gradient.
9. the preparation method of membrane electrode of fuel batter with proton exchange film according to claim 8, it is characterised in that the ladder
Degree formula network is that catalyst layer I increases successively to the electrochemistry specific surface area of catalyst layer II, and appearance features are porositys
Increased to catalyst layer II successively by catalyst layer I；The granule that the catalyst of catalyst layer I and binding agent are formed compares catalyst layer
The II granule closeness for being formed is high.
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| CN110289423A (en) * | 2019-05-17 | 2019-09-27 | 同济大学 | A kind of membrane electrode with catalyst gradient |
| CN110444791A (en) * | 2019-08-28 | 2019-11-12 | 深圳市通用氢能科技有限公司 | Catalyst coat film, fuel cell and preparation method |
| CN111129530B (en) * | 2019-12-31 | 2022-02-18 | 一汽解放汽车有限公司 | Catalytic slurry, membrane electrode, preparation method and application thereof |
| CN111313061A (en) * | 2020-02-28 | 2020-06-19 | 先进储能材料国家工程研究中心有限责任公司 | Fuel cell membrane electrode and preparation method thereof |
| CN114628694A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method and application of membrane electrode |
| CN113921829B (en) * | 2021-10-11 | 2023-09-15 | 中汽创智科技有限公司 | Anode catalyst layer, membrane electrode and preparation method thereof |
| CN115064715B (en) * | 2022-06-28 | 2023-10-27 | 浙江锋源氢能科技有限公司 | Membrane electrode CCM and preparation method thereof, membrane electrode assembly MEA and fuel cell |
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Address after: Zuchongzhi road Kunshan city 215300 Suzhou City, Jiangsu province No. 1699 Industrial Technology Research Institute building room 803 Co-patentee after: Jiangsu Yanchang sanglaite new energy Co., Ltd Patentee after: KUNSHAN INNOVATION RESEARCH INSTITUTE OF NANJING University Address before: Zuchongzhi road Kunshan city 215300 Suzhou City, Jiangsu province No. 1699 Industrial Technology Research Institute building room 803 Co-patentee before: KUNSHAN SUNLAITE NEW ENERGY Co.,Ltd. Patentee before: KUNSHAN INNOVATION RESEARCH INSTITUTE OF NANJING University |